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CN104684951B - The method for preparing the porous material based on isocyanates - Google Patents

The method for preparing the porous material based on isocyanates Download PDF

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Publication number
CN104684951B
CN104684951B CN201380050391.1A CN201380050391A CN104684951B CN 104684951 B CN104684951 B CN 104684951B CN 201380050391 A CN201380050391 A CN 201380050391A CN 104684951 B CN104684951 B CN 104684951B
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component
weight
amine
solvent
porous material
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CN104684951A (en
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M·弗力可
M·埃尔宾
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3237—Polyamines aromatic
    • C08G18/3243—Polyamines aromatic containing two or more aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0091—Aerogels; Xerogels

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The present invention relates to a kind of method for preparing porous material, and it includes making at least one polyfunctional isocyanate react in the presence of at least one catalyst and a kind of solvent with least one multifunctional aromatic amine.The purposes being particularly applied to the invention further relates to thus obtained porous material and the porous material as heat-barrier material in building field and vacuum insulation panel.

Description

The method for preparing the porous material based on isocyanates
The present invention relates to a kind of method for preparing porous material, it include making at least one polyfunctional isocyanate with least A kind of multifunctional aromatic amine reacts in the presence of at least one catalyst and solvent.The invention further relates to can obtain in this way Porous material, and purposes of the porous material as heat-barrier material, especially in building field and vacuum insulation panel In application.
Consider that there is several microns or significantly lower of hole size and the porous material of at least 70% high porosity based on theory Expect that (such as foam of polymers) is particularly preferred insulator.
This porous material with small average pore size can be, for example, passing through sol-gel process and subsequent drying And the organic aerogel or the form of xerogel prepared.In sol-gel process, prepare first based on before reactive organogel The colloidal sol of body, then the colloidal sol gelling is set to form gel by cross-linking reaction.In order to by gel obtain porous material (such as Aeroge), it is necessary to remove liquid.For the sake of simplicity, hereinafter the step is referred to as drying.
WO 2011/069959, WO 2012/000917 and WO 2012/059388 are described based on polyfunctional isocyanate With the porous material of multifunctional aromatic amine, wherein, the amine component includes multifunctional substituted aromatic amine.The porous material passes through Isocyanates is set to be reacted and be prepared in the solvent inert to isocyanates with the desired amount of amine.The use of catalyst is Know in WO 2012/000917 and WO 2012/059388.However, these documents, which disclose, includes only a small amount of conventional catalyst Preparation use.
It is well known, however, that the porous material based on polyureas material property, especially mechanical stability and/or compression strength And thermal conductivity is not all satisfactory in all applications.Especially, the thermal conductivity under ventilation state is not low enough.In perforate material In the case of material, the ventilation state is the state under environment atmospheric pressure, but in part closed pore or whole closed-cell materials In the case of (such as hard polyurethane foams), this state only after aging, after in hole, gas is gradually completely replaced Realize.
The particular problem of preparation based on isocyanates and amine known in the art is mixing defect.Mix the hair of defect Life is due to the high reaction rate of NCO and amino, because gelling reaction has been carried out very before being thoroughly mixed For a long time.Mixing defect causes porous material to have uneven and unsatisfactory material property.Therefore usually require to reduce Mix the theory of defect phenomenon.
Therefore, it is an object of the present invention to avoid disadvantages mentioned above.Especially, there is provided one kind without disadvantages mentioned above or Porous material with the disadvantages mentioned above for reducing degree.Compared to prior art, the porous material should have under low pressure to be changed The thermal conductivity entered.Notably, however, the porous material should (i.e. at atmosheric pressure) be led under ventilation state with low-heat Rate.In addition, the porous material should have high porosity, low-density and sufficiently high mechanical stability simultaneously.
Finally, should avoid mixing defect and so as to avoid in isocyanates and the structure of the porous material formed in amine reaction With the inhomogeneities of material property.
Accordingly, it has been found that the method for the present invention and the porous material that can be obtained in this way.The present invention's is porous Material is preferably aeroge or xerogel, specifically for aeroge.
The inventive method for preparing porous material includes reacting following component：
(a1) 25-94.9 weight % at least one polyfunctional isocyanate, and
(a2) 0.1-30 weight % at least one multifunctional aromatic amine with formula I
Wherein R1And R2It can be same or different, and be each independently selected from hydrogen and straight with 1 to 6 carbon atom Chain or branched alkyl, and all substituent Q1To Q5And Q1’To Q5’To be same or different, and be each independently selected from hydrogen, Primary amino radical and the straight or branched alkyl with 1 to 12 carbon atom, wherein the alkyl can carry other functional groups, condition is At least two primary amino radicals, wherein Q are included with compounds of formula I1、Q3And Q5In it is at least one be primary amino radical and Q1’、Q3’ And Q5’In it is at least one be primary amino radical,
(a3) 0-15 weight % water, and
(a4) 5-30 weight % at least one catalyst,
The gross weight meter of component (a1) to (a4) is based under each case, the wherein weight % of component (a1) to (a4) is amounted to For 100 weight %, and react and carried out in the presence of solvent (C), the solvent (C) removes after completion of the reaction.
Preferred embodiment can be found in claims and specification.The combination of preferred embodiment is without departing from this The scope of invention.
It is described in more detail below the preferred embodiment of component used.
Hereinafter, polyfunctional isocyanate is referred to as component (a1).Similarly, hereinafter, polyfunctional amine (a2) is united Referred to as component (a2).Those of ordinary skill in the art it should be clear that mentioned monomer component be present in the form of reacting it is porous In material.
For the purpose of the present invention, the degree of functionality of compound is the number of per molecule reactive group.In monomer component (a1) in the case of, degree of functionality is the number of per molecule NCO.In the case of monomer component (a2) amino, function Degree is the number of per molecule reactive amino.The degree of functionality of polyfunctional compound is at least 2.
If the mixture using the compound of different degrees of functionality exists as component (a1) or (a2), the degree of functionality of component Drawn under each case by the average of each compound degree of functionality.Polyfunctional compound's per molecule includes at least two above-mentioned functions Group.
For the purpose of the present invention, xerogel is the porous material prepared by sol-gel process, in the colloidal sol-solidifying In glue method, liquid phase by under less than the critical-temperature of liquid phase and critical pressure (" undercritical conditions ") dry and from gel Middle removing.Aeroge is the porous material prepared by sol-gel process, and in the sol-gel process, liquid phase is super Removed under critical condition from gel.
Preferably, reaction is carried out using each component of following amount：35-93.8 weight %, particularly 40-92.6 weight %'s Component (a1), 0.2-25 weight %, particularly 0.4-23 weight % component (a2), particularly 0-10 weight %, 0-9 weight % Water, and 6-30 weight %, particularly 7-28 weight % component (a4), each case be based on component (a1) to (a4) it is total The weight % of weight meter, wherein component (a1) to (a4) adds up to 100 weight %.
It is particularly preferred that reaction is carried out using each component of following amount：50-92.5 weight %, particularly 57-91.3 weights Measure % component (a1), 0.5-18 weight %, particularly 0.7-16 weight % component (a2), particularly 0-8 weight %, 0-6 Weight % water, and 7-24 weight %, particularly 8-21 weight % component (a4), each case are based on component (a1) extremely (a4) the weight % of gross weight meter, wherein component (a1) to (a4) adds up to 100 weight %.
In above-mentioned preferred scope, gained gel is particularly stable and is not shunk in subsequent drying steps or only slight Shrink.
Component (a1)
In the method for the invention, at least one polyfunctional isocyanate reacts as component (a1).
Preferably, the dosage of component (a1) be at least 35 weight %, specifically at least 40 weight %, particularly preferably at least 45 weight %, in particular at least 57 weight %.Preferably, the dosage of component (a1) is at most 93.8 weight %, is especially at most 92.6 weight %, at most particularly preferably 92.5 weight %, especially it is at most 91.3 weight %, each case is based on component (a1) To the gross weight meter of (a4).
Possible polyfunctional isocyanate is aromatic isocyanate, aliphatic isocyanate, alicyclic isocyanate and/or virtue Aliphatic isocyanate.Such polyfunctional isocyanate is known per se or can prepared by this as known method. Especially, polyfunctional isocyanate is also used as mixture use so that component (a1) includes various more officials in the case Can isocyanates.Possibly as monomeric building blocks polyfunctional isocyanate's (a1) per molecule monomer component have two (under Referred to herein as diisocyanate) or more than two isocyanate groups.
Specially suitable polyfunctional isocyanate is diphenyl methane 2,2 '-diisocyanate, diphenyl methane 2,4 '-two Isocyanates and/or diphenyl methane 4,4 '-diisocyanate (MDI), naphthalene 1,5- diisocyanate (NDI), toluene 2,4- bis- Isocyanates and/or toluene 2,6- diisocyanate (TDI), 3,3 '-dimethyl diphenyl diisocyanate, 1,2- diphenylethanes Diisocyanate and/or PPDI (PPDI), trimethylene diisocyanate, tetramethylene diisocyanate, five Methylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate and/or the isocyanic acid of eight methylene two Ester, 2- methyl pentamethylene 1,5- diisocyanate, 2- ethylbutylenes Isosorbide-5-Nitrae-diisocyanate, pentamethylene 1, the isocyanides of 5- bis- Acid esters, butylidene Isosorbide-5-Nitrae-diisocyanate, 1- isocyanic acid acyl groups -3,3,5- trimethyl -5- isocyanic acid sulfonylmethyl hexamethylenes are (different Fluorine that ketone diisocyanate, IPDI), Isosorbide-5-Nitrae-bis- (isocyanic acid sulfonylmethyl) hexamethylene and/or double (the isocyanic acid acyl group first of 1,3- Base) hexamethylene (HXDI), hexamethylene Isosorbide-5-Nitrae-diisocyanate, 1- hexahydrotoluenes 2,4- diisocyanate and/or 1- methyl rings Hexane -2,6- diisocyanate, and dicyclohexyl methyl hydride -4,4 '-diisocyanate, the isocyanic acid of dicyclohexyl methyl hydride 2,4 '-two Ester and/or dicyclohexyl methyl hydride 2,2 '-diisocyanate.
As polyfunctional isocyanate (a1), preferably aromatic isocyanate.Particularly preferred component (a1) it is multifunctional different Cyanate is following embodiment：
I) polyfunctional isocyanate of toluene di-isocyanate(TDI) (TDI), particularly 2,4-TDI or 2,6-TDI or 2 are based on, 4-TDI and 2,6-TDI mixture；
Ii the polyfunctional isocyanate of methyl diphenylene diisocyanate (MDI), particularly 2,2 '-MDI or 2,4) are based on '-MDI or 4,4 '-MDI or oligomeric MDI (also known as polyphenyl polymethylene isocyanates), or the isocyanide of above-mentioned diphenyl methane two Two or three of mixture of acid esters, or the thick MDI obtained in MDI preparation, or at least one MDI oligomer with extremely A kind of few mixture of above-mentioned low molecule amount MDI derivatives；
Iii) at least one embodiment i) aromatic isocyanate and at least one embodiment ii) aromatics isocyanic acid The mixture of ester.
Particularly preferred oligomeric methylene diphenyl diisocyanate is as polyfunctional isocyanate.Oligomeric methylene diphenyl two is different Cyanate (hereinafter referred to oligomeric MDI) is oligomeric condensation product or the mixture of a variety of oligomeric condensation products, therefore is hexichol The derivative of dicyclohexylmethane diisocyanate (MDI).The polyfunctional isocyanate preferably can also be by the isocyanic acid of monomer aromatic two The mixture of ester and oligomeric MDI forms.
Oligomeric MDI includes one or more MDI condensation product, its have it is polycyclic, and degree of functionality be more than 2, particularly 3 or 4 or 5.Oligomeric MDI is known and commonly known as polyphenyl polymethylene isocyanates or polymeric MDI.Oligomeric MDI is usual It is made up of the mixture of the isocyanates based on MDI with different degrees of functionality.Oligomeric MDI is generally used in mixed way with monomer MDI.
(average) degree of functionality of isocyanates comprising oligomeric MDI can about 2.2 to about 5, particularly 2.4-3.5, especially It is to change in the range of 2.5-3.The mixture of the polyfunctional isocyanate based on MDI with different degrees of functionality specifically for The thick MDI obtained in MDI preparation.
The mixture of polyfunctional isocyanate or a variety of polyfunctional isocyanates based on MDI be known and for example by BASF Polyurethanes GmbH are with trade nameSale.
The degree of functionality of component (a1) is preferably at least 2, specifically at least 2.2 and particularly preferably at least 2.5.Component (a1) Degree of functionality be preferably 2.2-4 and particularly preferably 2.5-3.
The content of NCO is preferably 5-10mmol/g, particularly 6-9mmol/g, particularly preferred 7- in component (a1) 8.5mmol/g.Those of ordinary skill in the art are, it is known that the content of NCO in terms of mmol/g and the working as when gauge with g/ Weight is measured into reciprocal relation.The content of NCO in terms of mmol/g can be according to ASTM D-5155-96A by with weight % The content of meter obtains.
In preferred embodiments, component (a1) is selected from following polyfunctional isocyanate comprising at least one：Diphenyl Methane 4,4 '-diisocyanate, diphenyl methane 2,4 '-diisocyanate, diphenyl methane 2,2 '-diisocyanate and oligomeric Methyl diphenylene diisocyanate.In the preferred embodiment, component (a1) particularly preferably includes oligomeric methylene diphenyl two Isocyanates and degree of functionality is at least 2.5.
The viscosity of component (a1) used can change in wide scope.The viscosity of component (a1) is preferably 100- 3000mPa.s, particularly preferred 200-2500mPa.s.
Component (a2)
According to the present invention, at least one multifunctional substitution aromatic amine (a2) with formula I is made in the presence of solvent (C) Reacted for component (a2)
Wherein R1And R2It can be same or different, and be each independently selected from hydrogen and with 1 to 6 carbon atom Straight or branched alkyl, and all substituent Q1To Q5And Q1’To Q5’It is same or different, and is each independently selected from Hydrogen, primary amino radical and the straight or branched alkyl with 1 to 12 carbon atom, wherein the alkyl can carry other functional groups, Condition is to contain at least two primary amino radicals, wherein Q with compounds of formula I1、Q3And Q5In it is at least one for primary amino radical and Q1’、Q3’And Q5’In it is at least one be primary amino radical.
In a preferred embodiment, Q is selected2、Q4、Q2’And Q4’So that with compounds of formula I with least one Individual straight or branched alkyl, the alkyl have 1 to 12 carbon atom and positioned at the α at least one primary amino radical for being bonded to aromatic ring On position, the alkyl can carry other functional groups.In this case, component (a2) includes multifunctional aromatic amine (a2-s).
For the purpose of the present invention, polyfunctional amine is that per molecule has at least two pairs of reactive amino of isocyanates Amine.Herein, primary amino radical and secondary amine are typically much higher than secondary amine to isocyanates in reactivity, the reactivity of primary amino radical Reactivity.
The dosage of component (a2) is preferably at least 0.2 weight %, specifically at least 0.4 weight %, particularly preferred at least 0.7 Weight %, in particular at least 1 weight %.The dosage of component (a2) preferably up to 25 weight %, especially be at most 23 weight %, Particularly preferably it is at most 20 weight %, is especially at most 18 weight %, the gross weight of component (a1) to (a4) is based under each case Gauge.In embodiment very particularly preferably, the dosage of component (a2) is at least 5 weight % and at most 20 weight %, base In component (a1) to (a4) gross weight meter.
According to the present invention, the R in formula I1And R2To be same or different, and it is each independently selected from hydrogen, primary amino radical With the straight or branched alkyl with 1 to 6 carbon atom.Preferably, R1And R2Selected from hydrogen and methyl.Particularly preferably R1=R2 =H.
In particularly preferred embodiments, Q is selected2、Q4、Q2’And Q4’So that substitution aromatic amine (a2-s) includes at least two Individual primary amino radical, wherein in each case, one or two has the straight or branched alkyl of 1 to 12 carbon atom positioned at bonding To the α positions of the primary amino radical of aromatic ring, wherein the alkyl optionally carries other functional groups.If select Q2、Q4、Q2’And Q4’ One or more of so that they correspond to the straight or branched with 1 to 12 carbon atom and with other functional groups Alkyl, then preferred amino and/or hydroxyl and/or halogen atom are as such functional group.
--- it is used in combination --- and is brought with the component (a4) described in greater detail below by the above-mentioned alkyl positioned at α positions The reduction of activity causes to produce the particularly preferred particularly stable gel of thermal conductivity under ventilation state.
Alkyl as substituent Q in formula I is preferably selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, Zhong Ding Base and the tert-butyl group.
Preferably, the amine (a2-s) be selected from 3,3 ', 5,5 '-tetraalkyl -4,4 '-diaminodiphenyl-methane, 3,3 ', 5, 5 '-tetraalkyl -2,2 '-diaminodiphenyl-methane and 3,3 ', 5,5 '-tetraalkyl -2,4 '-diaminodiphenyl-methane, wherein Alkyl in 3,3 ', 5 and 5 ' positions can be same or different, and be each independently selected from 1 to 12 carbon atom Straight or branched alkyl and other functional groups can be carried.Preferably, abovementioned alkyl is methyl, ethyl, n-propyl, isopropyl Base, normal-butyl, sec-butyl or the tert-butyl group (unsubstituted in each case).
In one embodiment, one of substituent Q one or more alkyl, more than one or all hydrogen atoms can Substituted by halogen atom (especially chlorine).Or one of substituent Q one or more alkyl, more than one or all hydrogen it is former Son can be by NH2Or OH substitutions.However, the alkyl in formula I is preferably made up of carbon and hydrogen.
In particularly preferred embodiments, component (a2) include 3,3 ', 5,5 '-tetraalkyl -4,4 '-diamino-diphenyl Methane, wherein alkyl can be same or different, and be each independently selected from 1 to 12 carbon atom and can be with Optionally with the straight or branched alkyl of functional group.Abovementioned alkyl is preferably selected from unsubstituted alkyl, particularly methyl, second Base, n-propyl, isopropyl, normal-butyl, sec-butyl and the tert-butyl group, particularly preferred methyl and ethyl.Very particularly preferably 3,3 ', 5, 5 '-tetraethyl -4,4 '-diaminodiphenyl-methane and/or 3,3 ', 5,5 '-tetramethyl -4,4 '-diaminodiphenyl-methane.
The polyfunctional amine of above-mentioned (a2-s) type is known for those of ordinary skills in itself or can led to Cross known method preparation.A kind of known method is that aniline or anil (are particularly 2,4- in the presence of acid catalyst Dialkyl aniline or 2,6- dialkyl anilines) with the reaction of formaldehyde.
Component (a2) can also optionally include the multifunctional aromatic amine (a2-u) different from the amine of structure (a2-s).It is described Aromatic amine (a2-u) preferably has the amino being only bonded with aromatic group, but can also and aromatics aliphatic with while with (ring) The reactive amino of group bonding.
Especially, suitable multifunctional aromatic amine (a2-u) is the isomers and derivative of diaminodiphenyl-methane.It is excellent Be elected to be the diaminodiphenyl-methane of the composition for component (a2) isomers or derivative specifically for 4,4 '-diamino-diphenyl Methane, 2,4 '-diaminodiphenyl-methane, 2,2 '-diaminodiphenyl-methane and oligomeric diamino diphenyl methane.
Especially, other suitable multifunctional aromatic amines (a2-u) are the isomers and derivative of toluenediamine.It is preferred that make Isomers and derivative for the toluenediamine of the composition of component (a2) is specifically for Toluene-2,4-diisocyanate, 4- diamines and/or Toluene-2,4-diisocyanate, 6- bis- Amine and diethyl toluene diamine, specifically for 3,5- diethyltoluenes -2,4- diamines and/or 3,5- diethyltoluene -2,6- diamines.
In the first particularly preferred embodiment, component (a2) is only made up of the multifunctional aromatic amine of (a2-s) type. In two preferred embodiments, component (a2) includes (a2-s) type and the multifunctional aromatic amine of (a2-u) type.In the latter --- second is excellent Select embodiment --- in, component (a2) preferably comprises at least a kind of multifunctional aromatic amine (a2-u), multifunctional aromatic amine (a2- U) at least one is selected from the isomers and derivative of diaminodiphenyl-methane (MDA).
In the second preferred embodiment, component (a2) correspondingly particularly preferably includes and is selected from following at least one more officials Can aromatic amine (a2-u)：4,4 '-diaminodiphenyl-methane, 2,4 '-diaminodiphenyl-methane, 2,2 '-diamino-diphenyl Methane and oligomeric diamino diphenyl methane.
Oligomeric diamino diphenyl methane includes the aniline of one or more methylene-bridgings and the condensation product of formaldehyde, It has multiple rings.Oligomeric MDA include degree of functionality be more than 2, specifically for 3 or 4 or 5 MDA at least one oligomer, but generally For degree of functionality be more than 2, specifically for 3 or 4 or 5 MDA a variety of oligomer.Oligomeric MDA is known or can be by itself Prepared for known method.Oligomeric MDA is used generally in the form of with monomer MDA mixture.
(average) degree of functionality of polyfunctional amine (a2-u) containing oligomeric MDA can be in about 2.3- about 5, especially 2.3-3.5 And change in the range of particularly 2.3-3.Especially, the mixture of the polyfunctional amine based on MDA with different degrees of functionality is It is generally thick via being formed in the aniline and formaldehyde condensation processes of hydrochloric acid catalysis as intermediate in thick MDI preparation MDA。
In above-mentioned preferable second embodiment, particularly preferably contain oligomeric diamino diphenyl methane as compound (a2-u) and total degree of functionality be at least 2.1 component (a2).
The ratio of (a2-s) type amine with formula I is preferred 10-100 weight %, is particularly 30-100 weight %, very Particularly preferred 50-100 weight %, especially 80-100 weight %, the gross weight meter of all polyfunctional amines based on component (a2), Therefore gross weight adds up to 100 weight %.
Different from (a2-s) type amine, the ratio of multifunctional aromatic amine (a2-u) is preferred 0-90 weight %, specifically for 0-70 Weight %, particularly preferred 0-50 weight %, in particular 0-20 weight %, the gross weight of all polyfunctional amines based on component (a2) Meter.
Component a3
Component (a3) is water.If using water, the dosage of preferable water is at least 0.01 weight %, especially at least 0.1 weight %, particularly preferably at least 0.5 weight %, especially at least 1 weight %.If using water, the dosage of preferable water At most 15 weight %, in particular up to 13 weight %, particularly preferably at most 11 weight %, especially up to 10 weight %, non- Often particularly preferably at most 9 weight %, especially up to 8 weight %, the gross weight of component (a1) to (a4) is based under each case (it is 100 weight %) counts.
The amino content being computed can be by following methods by water content and the reactive isocyanate base of component (a1) Content obtain：Assuming that the NCO of water and component (a1) reacts the amino for forming respective numbers completely, and by the content (total n is added with the content obtained by component (a2)Amine).Hereinafter, the remaining NCO bases n being computedNCOWith being computed The gained of amino through being formed and being used use ratio be referred to as calculate use than nNCO/nAmine, and it is equivalent proportion, i.e., each official The mol ratio that can be rolled into a ball.
Water and NCO react to form amino and discharge CO2.Therefore polyfunctional amine part produces (former as intermediate Position).In further course of reaction, they react to form urea linking group with NCO.Generation of the amine as intermediate Cause porous material that there is extra high mechanical stability and lower thermal conductivity.However, the CO formed2Gelling must not be disturbed, So that the structure of gained porous material is impacted in an undesired manner.These give the above-mentioned preferable water content upper limit, base Gross weight meter in (a1) to (a4).
In the case, use is calculated than (equivalent proportion) nNCO/nAminePreferably 1.01-5.The equivalent proportion is particularly preferably 1.1-3, specifically for 1.1-2.In this embodiment, nNCOTo nAmineExcess cause in dissolving agent process is removed porous material (special Not xerogel) contraction it is lower, and due to the cooperative interaction of catalyst (a4) cause improve network structure and lead Cause the improved final performance of gained porous material.
Component (a1) to (a4) is referred to generically hereinafter as organogel precursor (A).It is aobvious for those of ordinary skill in the art and It is clear to, the partial reaction of component (a1) to (a4) produces the true gel precursors (A) for being subsequently converted to gel.
Catalyst (a4)
The dosage of component (a4) is preferably at least 6 weight %, specifically at least 7 weight %, particularly preferably at least 8 weights Measure %, especially at least 9 weight %.The dosage of component (a4) preferably at most 30 weight %, in particular up to 28 weight %, spy Not preferably up to 24 weight %, especially up to 21 weight %, the gross weight meter of component (a1) to (a4) is based under each case.
It is, in principle, possible to catalyst be all catalyst known to persons of ordinary skill in the art, it can accelerate isocyanide The reaction (being referred to as gelation catalyst) of the trimerization reaction (being referred to as catalyst for trimerization) and/or isocyanates and amino of acid esters And/or the reaction (being referred to as kicker) of isocyanates and water.
Corresponding catalyst sheet as known, and just above-mentioned three kinds react for there is different relative activities.Root According to relative activity, thus catalyst can be classified as the one or more of the above-mentioned type.It is in addition, known to persons of ordinary skill in the art It is, it is also possible to the reaction in addition to those described above is reacted occurs.
Corresponding catalyst can especially characterize according to its gelling/blowing ratio, it is known that in such as Polyurethane, the 3rd Version, G.Oertel, Hanser Verlag, Munich, 1993.
Preferable catalyst (a4) has gelling/blowing ratio of balance, so that component (a1) and the reaction of water be not violent Accelerate, so as to have a negative impact to network structure, also result in shorter gelling time so that demoulding time advantageously shortens. Likewise it is preferred that catalyst there is significant activity to trimerization reaction.This uniformity to network structure produces favorable influence, Cause particularly advantageous mechanical performance.
The catalyst, which can be incorporated in monomeric building blocks, (may be incorporated into catalyst (incorporatable Catalyst)) or can not be incorporated to.
The catalyst of component (a4) is suitable as in particular selected from primary amine, secondary amine and tertiary amine, pyrrolotriazine derivatives, organometallic Oxide, quaternary ammonium salt, the hydroxide of compound, metallo-chelate, organic phosphorus compound, particularly phospholene (phospholene) Ammonium, alkali and alkaline earth metal ions hydroxide, alkali and alkaline earth metal ions alkoxide and the metal salt of carboxylic acid ammonium and carboxylic acid.
Suitable organic phosphorus compound (the particularly oxide of phospholene) is, such as 1- methylphospholenes oxide, 3- Methyl isophthalic acid-phenyl phospholene oxides, 1- phenyl phospholene oxides, 3- methyl isophthalic acids-benzyl phospholene oxides.
Preferably, suitable catalyst is catalyst for trimerization.Suitable catalyst for trimerization specifically for alkali catalyst, such as Quaternary ammonium base, there is the tetra-alkyl ammonium hydroxide and benzyltrimethylammonium hydroxide of 1-4 carbon atom such as in alkyl；Alkali metal hydrogen Oxide, such as potassium hydroxide or sodium hydroxide；And alkali metal alcoholates, such as sodium methoxide, potassium ethoxide and caustic alcohol and potassium isopropoxide.
Especially, other suitable catalyst for trimerization are the ammonium salt and metal salt for the carboxylic acid being further illustrated below, and N- hydroxyalkyl quaternary ammonium carboxylates, such as trimethyl hydroxypropyl ammonium formate.
Tertiary amine itself is also known for those of ordinary skills as catalyst for trimerization.Tertiary amine, that is, have There is the compound of at least one tertiary amino, particularly preferable as catalyst (a4).As catalyst for trimerization, unique energy Suitable tertiary amine is specifically for N, N', N "-three (dialkyl aminoalkyl)-s- Hexahydrotriazines, such as (dimethylamino of N, N', N "-three Base propyl group)-s- Hexahydrotriazines, three (dimethylaminomethyl) phenol.
Metallo-organic compound is known per se for those of ordinary skills as gelation catalyst.It is special Not preferred organo-tin compound, such as 2 ethyl hexanoic acid tin and dibutyl tin laurate.
Tertiary amine itself is also known for those of ordinary skills as gelation catalyst.As described above, Tertiary amine is particularly preferable as catalyst (a4).As gelation catalyst, there are the suitable tertiary amines of superperformance specifically for N, N- bis- Methyl-benzyl amine, N, N'- lupetazins and N, N- dimethylcyclohexylam,ne and dimethylcyclohexylam,ne, double (2- dimethyl Amino-ethyl) ether, N, N, N, N, N- five methyl diethylentriamines, methylimidazole, methylimidazole, aminopropylimidazol, two (1,4- diazas are double for methyl-benzyl amine, the carbon -7- alkene of 1,6- diazabicyclos [5.4.0] 11, triethylamine, triethylenediamine Ring [2.2.2] octane), dimethylaminoethanol amine, dimethylaminopropyl amine, N, N- dimethyl amino ethoxy ethanols, N, N, N- trimethylaminoethyl group monoethanolamine, triethanolamine, diethanol amine, triisopropanolamine, diisopropanolamine (DIPA), methyl diethanolamine And butyl diethanolamine.
Dimethylcyclohexylam,ne, lupetazin, double (2- dimethyl are selected from particularly preferable as the catalyst of component (a4) Amino-ethyl) ether, N, N, N, N, N- five methyl diethylentriamines, methylimidazole, methylimidazole, aminopropylimidazol, two Methyl-benzyl amine, the carbon -7- alkene of 1,6- diazabicyclos [5.4.0] 11, three dimethylamino-propylhexahydrotriaz,nes, triethylamine, Three (dimethylaminomethyl) phenol, triethylenediamine (diazabicyclo [2.2.2] octane), dimethylaminoethanol amine, Dimethylaminopropyl amine, N, N- dimethyl amino ethoxy ethanols, N, N, N- trimethylaminoethyl groups monoethanolamine, three ethanol Amine, diethanol amine, triisopropanolamine, diisopropanolamine (DIPA), methyl diethanolamine, butyl diethanolamine, metal acetylacetonates, Thylhexoic acid ammonium and metal ethyl hexyl hydrochlorate.Very particularly preferably dimethylcyclohexylam,ne, lupetazin, methylimidazole, two Methylimidazole, dimethyl benzyl amine, the carbon -7- alkene of 1,6- diazabicyclos [5.4.0] 11, three dimethylaminopropyl hexahydros three Piperazine, triethylamine, three (dimethylaminomethyl) phenol, triethylenediamine (diazabicyclo [2.2.2] octane), dimethylamino Ethylethanolamine, dimethylaminopropyl amine, N, N, N- trimethylaminoethyl groups monoethanolamine, triethanolamine, diethanol amine, methyl two Monoethanolamine, butyl diethanolamine, thylhexoic acid ammonium and metal ethyl hexyl hydrochlorate.
In addition, carboxylate is very particularly preferably used as catalyst.Preferable carboxylate is with alkali metal ion, alkaline earth gold Belong to ion or ammonium ion as cation, i.e., they are the corresponding salt of carboxylic acid.Preferable carboxylate is formates, acetate, 2- Ethyl hexyl hydrochlorate, trifluoroacetate, adipate, benzoate and with 10-20 carbon atom and optionally in side base Saturation or unsaturated hard soap with OH bases.
Catalyst very particularly preferably is selected from potassium formate, sodium acetate, potassium acetate, cesium acetate, 2 ethyl hexanoic acid potassium, trifluoro Potassium acetate, Potassium Adipate, sodium benzoate and saturation with 10-20 carbon atom and with OH bases optionally in side base or The alkali metal salt of unsaturated hard soap.
According to the present invention, react and carried out in the presence of solvent (C).
For the purpose of the present invention, term solvent (C) includes liquid diluent, i.e., not only included solvent in the narrow sense but also including Decentralized medium.Especially, mixture can be true solution, colloidal solution or dispersion (such as emulsion or suspension).Mixture is excellent Elect true solution as.The compound that it is liquid under conditions of step (a) that solvent (C), which is, preferable organic solvent.
In principle, solvent (C) can be the mixture of organic compound or multiple compounds, and solvent (C) carries in step (a) For being liquid under the temperature and pressure condition (abbreviation dissolution conditions) of the mixture.Select the composition of solvent (C) so that it can Dissolving disperses, preferably dissolves organic gel precursors.Preferable solvent (C) is that of the solvent as organogel precursor (A) A bit, i.e., those of organogel precursor (A) are completely dissolved at reaction conditions.
The reaction product reacted in the presence of solvent (C) is initially gel, i.e., by the viscoplasticity chemistry of solvent (C) swelling Network (viscoelastic chemical network).For the solvent of the good sweller of the network of formation in step (b) (C) network with micropore and small average pore size is typically resulted in, and is the solvent of the poor sweller of gel caused by step (b) (C) macropore (coarse-pored) network with big average pore size is typically resulted in.
Therefore the selection of solvent (C) influences required pore-size distribution and required porosity.The selection of solvent (C) is generally also Carry out as follows：Unknown explict occurrence is by the reaction product that precipitates during or after (b) is carried out the inventive method the step of Formation caused by precipitation or flocculation.
When selecting suitable solvent (C), the ratio of the reaction product of precipitation is typically smaller than 1 weight %, based on mixture Gross weight meter.The amount of the precipitated product formed in the specific solvent (C) can by before gel point by reactant mixture Filtered by suitable filter to be determined by gravimetry.
Possible solvent (C) is by the solvent for the polymer based on isocyanates known in the art.Preferably Solvent is used as those of the solvent of component (a1) to (a4), i.e., is almost completely dissolved component (a1) to (a4) at reaction conditions Composition solvent.Solvent (C) preferred pair component (a1) is inert, i.e., non-reacted.
Possible solvent (C) is, for example, ketone, aldehyde, chain acid alkyl ester, acid amides (such as formamide and N- crassitudes Ketone), sulfoxide (such as dimethyl sulfoxide (DMSO)), aliphatic series and cyclic aliphatic halogenated hydrocarbons, halogenated aromatic compound and fluorine-containing ether.It is also likely to be two kinds Or the mixture of a variety of above-claimed cpds.
Other are acetals possibly as solvent (C), especially diethoxymethane, dimethoxymethane and 1,3- dioxy Penta ring.
Dialkyl ether and cyclic ethers are also suitable as solvent (C).Preferable dialkyl ether is specifically for 2-6 carbon atom Those, particularly methyl ethyl ether, Anaesthetie Ether, methyl-propyl ether, methyl isopropyl ether, ethyl ether, ethylisopropyl Base ether, dipropyl ether, propyl isopropyl ether, Di Iso Propyl Ether, methyl butyl ether, methyl-isobutyl ether, methyl tertiary butyl ether(MTBE), second Base n-butyl ether, ethyl isobutyl ether and ethyl tert-butyl ether (ETBE).Preferable cyclic ethers is specifically for tetrahydrofuran, dioxanes and tetrahydrochysene pyrrole Mutter.
Aldehyde and/or ketone are particularly preferable as solvent (C).Especially, the aldehyde and ketone for being suitable as solvent (C) correspond to lead to Formula R2-(CO)-R1Those, wherein R1And R2Respectively hydrogen or the alkyl with 1,2,3 or 4 carbon atom.Especially, properly Aldehydes or ketones for acetaldehyde, propionic aldehyde, n-butanal, isobutylaldehyde, 2- ethyl butyraldehydes, valeral, isopentyl aldehyde, 2 methyl pentanal, 2- ethyl hexyls Aldehyde, methacrylaldehyde, MAL, crotonaldehyde, furfural, methacrylaldehyde dimer, MAL dimer, 1,2,3,6- tetrahydrochysene benzene Formaldehyde, 6- methyl -3- hexamethylenes aldehyde, cyanaldehyde, glyoxylic acid ethyl ester, benzaldehyde, acetone, methyl iso-butyl ketone (MIBK), metacetone, first Base ethyl ketone, methyl iso-butyl ketone (MIBK), methyl n-butyl ketone, ethyl isopropyl ketone, 2- acetyl furans, 2- methoxyl group -4- methyl are amyl- 2- ketone, cyclohexanone and acetophenone.Above-mentioned aldehyde and ketone can also mixture form use.With each substituent with up to The ketone and aldehyde of the alkyl of 3 carbon atoms are preferably as solvent (C).Particularly preferred methyl ethyl ketone.
Other preferable solvents are chain acid alkyl ester, particularly methyl formate, methyl acetate, Ethyl formate, acetic acid fourth Ester, ethyl acetate and ethyl acetoacetate.Particularly preferred ethyl acetate.Preferable halogenated solvent is documented in WO 00/24799, the The row of page 4 the 12nd is into the 4th row of page 5.
In many cases, especially suitable solvent (C) by using mixed form two or more be selected from it is above-mentioned molten The compound of the complete miscibility of agent and obtain.
Too many sufficiently stable gel will not be shunk in order to be obtained in step (b) in the drying process in step (c), Component (a1) to (a4) ratio generally have to be not less than 5 weight %, are based upon 100 weight % component (a1) to (a4) and molten The gross weight meter of agent (C).Component (a1) to (a4) ratio are preferably at least 6 weight %, particularly preferably at least 8 weight %, outstanding It is at least 10 weight %, is based upon 100 weight % component (a1) to (a4) and the gross weight meter of solvent (C).
On the other hand, the concentration of component (a1) to (a4) necessarily can not be too high in the mixture provided, because Otherwise there cannot be the porous material of advantageous property.In general, the ratio of component (a1) to (a4) is no more than 40 weight %, It is based upon 100 weight % component (a1) to (a4) and the gross weight meter of solvent (C).The ratio of component (a1) to (a4) is preferably not More than 35 weight %, particularly preferably it is no more than 25 weight %, especially no more than 20 weight %, is based upon 100 weight % component (a1) to (a4) and the gross weight meter of solvent (C).
The gross weight of component (a1) to (a4) than preferably 8-25 weight %, specifically for 10-20 weight %, particularly preferably 12-18 weight %, it is based upon 100 weight % component (a1) to (a4) and the gross weight meter of solvent (C).Follow in the scope The amount of interior starting material causes porous material to have the lower shrinkage of particularly advantageous pore structure, lower thermal conductivity and drying process.
Before reaction, it is necessary to mix component used, be particularly mixed uniformly.Mixing rate should be higher than that reaction rate To avoid mixing defect.Suitable mixed method is known for those of ordinary skills in itself.
Prepare the method for optimizing of porous material
In preferred embodiments, method of the invention comprises at least following steps：
(a) component (a1) to (a4) as described above and solvent (C) are provided,
(b) in the presence of solvent (C), component (a1) to (a4) reaction is made to form gel, and
(c) gel obtained in previous steps is dried.
The preferred embodiment of step (a) to (c) is described in detail below.
Step (a)
According to the present invention, component (a1) to (a4) and solvent (C) are provided in step (a).
Component (a1) and (a2) are preferably provided separately from each other, in the solvent (C) of each comfortable suitable partial amount.It is provided separately So that before combination with most preferably may monitor or control gelling reaction during mixing.
Component (a3) and (a4) provide particularly preferable as with the mixture of component (a2), i.e., are separately carried with component (a1) For.This is avoided when in the absence of component (a2), and water reacts with component (a1) or component (a4) forms network with component (a1) reaction. Water should mix in advance with component (a1), otherwise cause the unfavorable property in terms of the uniformity of loose structure and the thermal conductivity of resulting materials Energy.
The one or more mixtures provided in step (a) can also include known to persons of ordinary skill in the art normal Auxiliary agent is advised as other compositions.What be can be mentioned that is, such as surface reactive material, fire retardant, nucleator, oxidation stabilizers, lubrication It is agent and releasing agent, dyestuff and pigment, stabilizer (such as to resistant to hydrolysis, light, heat or the stabilizer of colour fading), inorganic and/or organic fill out Material, infrared light screening agent, reinforcing material and biocide.
The other information for being related to above-mentioned auxiliary agent and additive is found in technical literature, such as Plastics Additive Handbook, the 5th edition, H.Zweifel, ed.Hanser Publishers, Munich, 2001.
Step (b)
According to the present invention, in step (b), the reaction of component (a1) to (a4) occurs in the presence of solvent (C) with shape Into gel.In order to carry out the reaction it may first have to prepare the homogeneous mixture of the component provided in step (a).
Component is provided in step (a) to carry out in a usual manner.Mixer preferred for use herein or another mixing Equipment is to realize good and quickly mix.The time for causing to be at least a partially formed gel relative to gel reaction, prepare uniform Should be shorter the time required to mixture, to avoid mixing defect.Other mixing conditions are not usually crucial；For example, mixing can To be carried out under 0-100 DEG C and 0.1-10 bars (bar) (absolute), particularly carried out under such as room temperature and atmospheric pressure. After preparing homogeneous mixture, preferably mixing apparatus is turned off.
Gelling reaction is the addition polymerization of sudden reaction, specially NCO and amino.
For the purpose of the present invention, gel is the cross-linking system based on polymer, and it is contacted with liquid (is referred to as sol gel (Solvogel) or lyogel (Lyogel), or by the use of water it is used as liquid：Hydrogel (aquagel) or hydrogel (hydrogel)). Herein, polymer phase forms continuous three-dimensional network.
The inventive method the step of in (b), gel is generally formed by standing, for example, by simply making mixture Container, reaction vessel or reactor (be hereinafter referred to gelled device) the static formation at place.During gelling (gel-forming) It is preferred that the mixture is not stirred for or mixes, because this will hinder gel-forming.It has been found that covered during gelling Mixture or closing gelling equipment are favourable.
Gelling is known for those of ordinary skills in itself and is documented in such as WO-2009/ For the 19th row of page 027310,21 into the 13rd row of page 23, its content all includes this specification by way of citation.
Step (c)
According to the present invention, the gel obtained in previous steps is dried in step (c).
In preferred embodiments, drying is carried out at supercritical conditions, preferably by solvent CO2Or other are suitable to Carried out after the solvent displacement of supercritical drying purpose.This drying is known to persons of ordinary skill in the art in itself.It is super to face Condition expression liquid phase to be removed in boundary's is with temperature and pressure existing for supercriticality.Exist in this way, it is possible to reduce gelinite Remove contraction during solvent.
The supercritical drying of gel is carried out preferably in autoclave.Herein, particularly preferred supercritical CO2, that is, dry excellent Gated supercritical CO2Method extractant and carry out.Preferably, covered completely with organic solvent filling autoclave to gel first The degree of lid, therefore autoclave is closing.This can prevent to start in gel and supercritical CO2Due to organic solvent before contact The gel shrinks for evaporating and occurring.
In another embodiment, the drying of gained gel passes through below the critical-temperature of solvent (C) and critical pressure Temperature and pressure under solvent (C) be converted into gaseous state and carried out.Therefore, dry and be preferably present in by removing in reaction not have There is the solvent (C) replaced in advance with other solvents to carry out.
It is known and be documented in WO 2009/027310 that such method is similarly those of ordinary skill in the art, page 26 the For 22 rows into the 36th row of page 28, its content all includes this specification by way of citation.
The performance and purposes of porous material
The present invention also provides the porous material that can be obtained by the method for the present invention.For the purpose of the present invention, aeroge Preferably as porous material, i.e., the porous material that can be obtained according to the present invention is preferably aeroge.
Average pore size carries out figure by SEM and then using statistically significantly fairly large number of hole Determined as analysis.Corresponding method is known for those of ordinary skills.
The volumetric average pore footpath of porous material is preferably more than 4 microns.The volumetric average pore footpath of porous material is particularly preferred No more than 3 microns, very particularly preferably no more than 2 microns and especially no more than 1 micron.
Although for the angle of lower thermal conductivity, very small hole size and high porosity are preferable, from preparation For in order to obtain the angle of the porous material of enough mechanically stables, there is actual lower limit in volumetric average pore footpath.It is general and Speech, volumetric average pore footpath is at least 50nm, preferably at least 100nm.
The porosity for the porous material that can be obtained according to the present invention is preferably at least 70 volume %, particularly 70-99 bodies Product %, particularly preferably at least 80 volume %, very particularly preferably at least 85 volume %, especially 85-95 volumes %.With volume % The porosity of expression means porous material mesopore specific ratio of the total volume.Although for the angle of minimum thermal conductivity generally Very high porosity is needed, but the mechanical performance of porous material and processability are applied with the upper limit to porosity.
Component (a1) to (a3) and optionally (a4) (as long as can mix catalyst) is deposited in the form of reacting (polymer) In the porous material that can be obtained according to the present invention.Due to the composition of the present invention, monomeric building blocks (a1) and (a2) exist Mainly it is bonded in porous material by urea linking group and/or isocyanuric acid ester linking group, wherein isocyanurate group passes through The trimerization of the NCO of monomeric building blocks (a1) is formed.If porous material includes other components, other are possible Linking group is, for example, reacting the carbamate groups formed by NCO and alcohol or phenol.
The mol% of the linking group of monomeric building blocks measure is led under solid state or solvent swelling state in porous material Cross NMR spectroscopy (nuclear magnetic resonance) progress.Suitable assay method is known for those of ordinary skills.
Can be usually 20-600g/L, preferably 50-500g/L and especially according to the density of porous material that the present invention obtain It is preferred that 70-200g/L.
The method of the present invention obtains coherent porous material rather than just polymer powder or particle.Herein, gained The 3D shape of porous material is determined by the shape of gel, and the shape of gel is determined by the shape of gelling equipment.Therefore, example Such as, cylindric gelation vessels generally yield approximate columned gel, and it can then be dried and obtained with cylindrical shape Porous material.
Favourable hot property and favourable material property can be had according to the porous material that the present invention obtains, such as easily added Work and high mechanical stability, such as low fragility.The porous material is with low-density and in addition with small average pore size chi It is very little.The combination of above-mentioned performance cause the present invention material may be used as it is heat-insulated, particularly be used for vacuum insulation panel application Heat-barrier material and construction material；Good effect of heat insulation is especially advantageous in building material field under ventilation state.
Embodiment
Plane table (Lambda Control A50) the measure thermal conductivity λ for being purchased from Hesto is used according to DIN EN 12667.
Use following compound：
Component a1：
NCO content is 30.9g/100g (according to ASTM D-5155-96A), degree of functionality is that viscosity is at 3 or so and 25 DEG C 2100mPa.s (according to DIN 53018) oligomeric MDI (M200) (hereinafter referred to as " compound M200 ").
Component a2：
3,3 ', 5,5 '-tetraethyl -4,4 '-diaminodiphenyl-methane (hereinafter referred to as " MDEA ").
Catalyst a4：
Triethanolamine, triethylenediamine (IUPAC:1,4- diazabicyclos [2.2.2] octane) and methyl diethanolamine.
Embodiment 1
At 20 DEG C in glass beaker, 80g compound M200 is dissolved in 220g 2- butanone under agitation. In two glass beakers, 4g compound MDEA and 12g triethanolamines are dissolved in 220g 2- butanone.Step (a) will be come from Two kinds of solution mixing.Mixture clarified, low viscosity.Mixture is stood to 24 hours at room temperature to solidify. Then gel is taken out from glass beaker and supercritical CO is used in autoclave2Carried out by solvent extraction as described below Dry.
Gel monolith is taken out and is transferred in 250ml autoclave from glass beaker.Use purity>99% acetone is filled out Autoclave is filled so that monolithic is covered and with rear enclosed autoclave by acetone completely.By the monolithic in CO224 are dried in air-flow Hour.Pressure (drying in system) is in the range of 115-120 bars；Temperature is 40 DEG C.Finally, by the pressure in system at 40 DEG C At a temperature of be reduced to atmospheric pressure by about 45 minutes in a controlled manner.Open autoclave and take out dry monolithic.
The density of gained porous material is 168g/L.Thermal conductivity at 10 DEG C is 22.3mW/m*K.
Embodiment 2
At 20 DEG C in glass beaker, 80g compound M200 is dissolved in 250g ethyl acetate under agitation. In second glass beaker, 4g compound MDEA and 12g methyl diethanolamines are dissolved in 250g ethyl acetate.In the future Mixed from two kinds of solution of step (a).Mixture clarified, low viscosity.Mixture is stood to 24 hours at room temperature To solidify.In a manner of corresponding with embodiment 1, then gel is taken out and in autoclave using super from glass beaker Critical CO2It is dried by solvent extraction.
The density of gained porous material is 165g/L.Thermal conductivity at 10 DEG C is 20.9mW/m*K.
Embodiment 3
At 20 DEG C in glass beaker, 80g compound M200 is dissolved in 220g 2- butanone under agitation. In second glass beaker, 4g compound MDEA and 8g triethylenediamines are dissolved in 220g 2- butanone.Step will be come from Suddenly two kinds of solution mixing of (a).Mixture clarified, low viscosity.Mixture is stood to 24 hours at room temperature to send out Raw solidification.In a manner of corresponding with embodiment 1, then gel is taken out and in autoclave using overcritical from glass beaker CO2It is dried by solvent extraction.
The density of gained porous material is 155g/L.Thermal conductivity at 10 DEG C is 20.6mW/m*K.
Embodiment 4
At 20 DEG C in glass beaker, 48g compound M200 is dissolved in 220g 2- butanone under agitation. In second glass beaker, 8g compound MDEA and 8g metil-diethanolamines and 1g water are dissolved in 220g 2- butanone.Will Two kinds of solution mixing from step (a).Mixture clarified, low viscosity.It is small that mixture is stood to 24 at room temperature When to solidify.In a manner of corresponding with embodiment 1, then gel is taken out from glass beaker and used in autoclave Supercritical CO2It is dried by solvent extraction.
The density of gained porous material is 130g/L.Thermal conductivity at 10 DEG C is 19.5mW/m*K.
Embodiment 5C
At 20 DEG C in glass beaker, 80g compound M200 is dissolved in 220g 2- butanone under agitation. In second glass beaker, 4g compound MDEA and 1g triethanolamines are dissolved in 220g 2- butanone.Step (a) will be come from Two kinds of solution mixing.Mixture clarified, low viscosity.It is solid to occur that mixture is stood to 24 hours at room temperature Change.Gel has paste-like consistency and can not be stripped.
Embodiment 6C
At 20 DEG C in glass beaker, 80g compound M200 is dissolved in 220g 2- butanone under agitation. In second glass beaker, 4g compound MDEA and 3g triethanolamines are dissolved in 220g 2- butanone.Step (a) will be come from Two kinds of solution mixing.Mixture clarified, low viscosity.It is solid to occur that mixture is stood to 24 hours at room temperature Change.Gel has paste-like consistency and can not be stripped.
Embodiment 7C
At 20 DEG C in glass beaker, 80g compound M200 is dissolved in 250g ethyl acetate under agitation. In second glass beaker, 4g compound MDEA and 1g methyl diethanolamines are dissolved in 250g ethyl acetate.In the future Mixed from two kinds of solution of step (a).Mixture clarified, low viscosity.Mixture is stood to 24 hours at room temperature To solidify.Gel has paste-like consistency and can not be stripped.
Embodiment 8C
At 20 DEG C in glass beaker, 80g compound M200 is dissolved in 250g ethyl acetate under agitation. In second glass beaker, 4g compound MDEA and 2g methyl diethanolamines are dissolved in 250g ethyl acetate.In the future Mixed from two kinds of solution of step (a).Mixture clarified, low viscosity.Mixture is stood to 24 hours at room temperature To solidify.Gel has paste-like consistency and can not be stripped.
Embodiment 9C
At 20 DEG C in glass beaker, 80g compound M200 is dissolved in 220g 2- butanone under agitation. In second glass beaker, 4g compound MDEA and 1g triethylenediamines are dissolved in 220g 2- butanone.Step will be come from Suddenly two kinds of solution mixing of (a).Mixture clarified, low viscosity.Mixture is stood to 24 hours at room temperature to send out Raw solidification.Gel has paste-like consistency and can not be stripped.
Embodiment 10C
At 20 DEG C in glass beaker, 48g compound M200 is dissolved in 220g 2- butanone under agitation. In second glass beaker, 8g compound MDEA and 1g methyl diethanolamines and 1g water are dissolved in 220g 2- butanone.Will Two kinds of solution mixing from step (a).Mixture clarified, low viscosity.It is small that mixture is stood to 24 at room temperature When to solidify.Gel has paste-like consistency and can not be stripped.

Claims (18)

1. a kind of method for preparing porous material, methods described includes reacting following component：
(a1) 25-94.9 weight % at least one polyfunctional isocyanate, and
(a2) 0.1-30 weight % at least one multifunctional aromatic amine with formula I
Wherein R1And R2It can be same or different, and be each independently selected from hydrogen and the straight chain with 1 to 6 carbon atom Or branched alkyl, and all substituent Q1To Q5And Q1’To Q5’To be same or different, and it is each independently selected from hydrogen, primary Amino and the straight or branched alkyl with 1 to 12 carbon atom, condition is to contain at least two primary with compounds of formula I Amino, wherein Q1、Q3And Q5In it is at least one be primary amino radical and Q1’、Q3’And Q5’In it is at least one be primary amino radical,
Wherein select Q2、Q4、Q2’And Q4’So that with compounds of formula I with least one straight or branched alkyl, it is described Alkyl has 1 to 12 carbon atom and relative to being bonded at least one primary amino radical of aromatic ring on α positions；
Wherein with formula I multifunctional aromatic amine (a2) alkyl be selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, Sec-butyl and the tert-butyl group；With
(a4) 6-30 weight % at least one catalyst,
The weight of gross weight meter, wherein component (a1), (a2) and (a4) based on component (a1), (a2) and (a4) under each case Amount % adds up to 100 weight %, and reacts and carried out in the presence of solvent (C), and the solvent (C) is removed after completion of the reaction Go；
Wherein component (a4) is selected from primary amine, secondary amine and tertiary amine, pyrrolotriazine derivatives, metallo-organic compound, metallo-chelate, ring phosphorus The oxide of alkene, quaternary ammonium salt, ammonium hydroxide, alkali and alkaline earth metal ions hydroxide, alkali and alkaline earth metal ions alkoxide and carboxylic Hydrochlorate；
Wherein without using water.
2. the method for claim 1, it include making 35-93.8 weight % component (a1), 0.2-25 weight % component (a2), Reacted with 6-30 weight % component (a4), the gross weight meter of component (a1), (a2) and (a4), wherein group are based under each case (a1), (a2) and (a4) weight % is divided to add up to 100 weight %.
3. the method for claim 1 or 2, the dosage of wherein component (a2) is at least 5 weight % and at most 20 weight %, based on group Divide (a1), (a2) and (a4) gross weight meter.
4. the method for claim 1 or 2, it includes making 52-92.5 weight % component (a1), 0.5-18 weight % component (a2) and 7-24 weight % component (a4) reaction, the gross weight meter of component (a1), (a2) and (a4) is based under each case, The weight % of wherein component (a1), (a2) and (a4) adds up to 100 weight %.
5. at least one it is selected from following compound the method for claim 1 wherein amine component (a2) includes：3,3 ', 5,5 '-four Alkyl -4,4 '-diaminodiphenyl-methane, 3,3 ', 5,5 '-tetraalkyl -2,2 '-diaminodiphenyl-methane and 3,3 ', 5,5 ' - Tetraalkyl -2,4 '-diaminodiphenyl-methane, wherein the alkyl in 3,3 ', 5 and 5 ' positions can be same or different, and And independently selected from 1 to 12 carbon atom and can carry other functional groups straight or branched alkyl.
6. the method for claim 1 wherein the multifunctional aromatic amine (a2) with formula I be 3,3 ', 5,5 '-tetraalkyl -4,4 ' - Diaminodiphenyl-methane.
7. the method for claim 6, wherein the multifunctional aromatic amine (a2) with formula I is 3,3 ', 5,5 '-tetraethyl -4,4 ' - Diaminodiphenyl-methane and/or 3,3 ', 5,5 '-tetramethyl -4,4 '-diaminodiphenyl-methane.
8. the method for claim 1 wherein component (a4) be selected from dimethylcyclohexylam,ne, double (2- dimethyl aminoethyls) ethers, N, N, N, N, N- five methyl diethylentriamine, methylimidazole, methylimidazole, aminopropylimidazol, dimethyl benzyl amine, 1, Carbon -7- the alkene of 6- diazabicyclos [5.4.0] 11, three dimethylamino-propylhexahydrotriaz,nes, triethylamine, three (dimethylaminos Methyl) phenol, triethylenediamine (diazabicyclo [2.2.2] octane), dimethylaminoethanol amine, dimethylaminopropyl Amine, N, N- dimethyl amino ethoxy ethanols, N, N are N- trimethylaminoethyl groups monoethanolamine, triethanolamine, diethanol amine, three different Propanolamine, diisopropanolamine (DIPA), methyl diethanolamine, butyl diethanolamine, metal acetylacetonates, thylhexoic acid ammonium and metal Ethyl hexyl hydrochlorate.
9. the method for claim 1 wherein component (a4) is selected from alkali metal carboxylate, alkaline earth metal carboxylation and carboxylic acid ammonium.
10. the method for claim 1 wherein component (a4) includes 2 ethyl hexanoic acid potassium.
11. the method for claim 1, it includes：
A) component (a1), (a2), (a4) and solvent (C) defined in any one of claim 1 to 10 are provided,
B) in the presence of solvent (C), component (a1), (a2) and (a4) reaction is made to form gel, and
C) gel obtained in previous steps is dried.
12. the method for claim 11, wherein component (a1) are provided separately with component (a2) and (a4), in part under each case In the solvent (C) of amount.
13. the method for claim 11 or 12, wherein the drying of gained gel passes through the critical of the liquid in gel is contained in Under temperature and pressure below temperature and critical pressure, the liquid that will be contained in gel is converted into gaseous state and carried out.
14. the method for claim 11 or 12, wherein the drying of gained gel is carried out at supercritical conditions.
15. the method for claim 1 or 2, wherein component (a4) are selected from tertiary amine.
16. a kind of porous material, it is obtained by the method for any one of claim 1 to 15.
17. purposes of the porous material of claim 16 as heat-barrier material.
18. the porous material of claim 16 is used for the purposes of vacuum insulation panel.
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